Preparation of vinylidene chlorofluoride



PREPARATION or VINYLIDENE CHLOROFLUORIDE Erhard .l. Prill, Dayton, Ohio, assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application February 16, 1956 Serial No. 565,776

3 Claims. (Cl. 260-6535) I onsoon+nr omoohr II omoonr T on,=oo1r The present invention is also directed to a method of conducting reaction II above, in which a substantial portion of dichlorofluoroethane is pyrolyzed to vinylidene chlorofluoride, particularly at reaction temperatures of 465 to 535 C.

A method of conducting reaction I above, in which stannic fluoride on activated carbon or aluminum fluoride is used as a catalyst at fluorination temperatures, such as 60 to 150 C. is described and claimed in my copending application, Serial No. 565,777, filed of even date herewith.

One of the known prior art procedures for preparing vinylidene chlorofluoride involves the bromination of 1,1-dichloroethylene to 1,2-dibromo-2,2-dichloroethane,

.fluorination of the l,Z-dibromo-2,2-dichloroethane to 1- bromo-2,2-dichloro-2-fluoroethane by the addition of successive separate small portions of red mercuric oxideand anhydrous hydrogen fluoride, and then dehalogenation of the 1-bromo-2,2-dichloro-2-fluoro-ethane by the use of mossy zinc in anhydrous ethanol. Not only is this prior art procedure somewhat lengthy and tedious, but it is a series of batch reactions, while the simple vapor phase reactions of the present invention can readily be run as a continuous process. The present invention provides a simple 2-step procedure for convertingthe readily available methylchloroform to vinylidene chlorofluoride.

Pyrolysis is a known method of dehydrohalogenating and/or cleaving chlorofluoro compounds. However, in the pyrolysis of such compounds, it has been customary to employ high temperatures, such as 600 or 700 C. to 1000 C. By contrast, it has now been found that in order to obtain good conversions and yields in the pyrolysis of dichlorofluoroethane to vinylidene chlorofluoride it is necessary to use reaction temperatures of about 465 to 535 C. It has also been discovered that in the pyrolysis of dichlorofluoroethane it is necessary to use a reaction time of about to 60 seconds, and a reaction time of 25 to 45 seconds is preferable. The reaction time is the time that a unit volume of the reactants remains in the reactor tube. This contact time may be calculated by dividing the volume of the reactor by the volume of the gas charged (at reaction temperature), per second.

The reactor used-for the pyrolysis procedure was a 1 inch CD. by 42 inch nickel tube of 375 ml. volume packed with nickel helices. The nickel helices were used to aid the transfer of heat to the vapors passing through the tube. The reactor was in a position inclined about 10 from the vertical, but it can be used in a horiatent zontal, vertical or other position. Nickel was selected as the material for the tube and helices in order to have a reasonably economical material which would be fairly resistant to high temperatures and fluorine compounds. Moreover, if nickel, nickel chloride or nickel fluoride have any catalytic efiect, they probably promote the pyrolysis reaction. It is also possible to use other metals having possible catalytic effects for the tube and helices, e.g., aluminum, or to use a tube lined with a noble metal such as platinum, palladium or silver.

The same 1 x 42" nickel tube was used for the fluorination reaction, but in this case it was packed with catalyst rather than nickel helices.

EXAMPLE 1 A quantity of 1,l-dichloro-l-fluoroethane was placed in a reservoir which was connected successively through a needle valve, a rota-meter and a connecting tube to the nickel reactor tube. The connecting tube was provided with a side tube for the admission of nitrogen, and a section of the connecting tube adjacent to the nickel reactor tube was wrapped with Nichrome wire in order to have a heating means for a preliminary heating and vaporizing section. The nickel reactor tube was provided with a jacket for heating. At its discharge end, the reactor tube was connected to a connecting tube, which passed through a stopper into a vacuum flask and the lower end of the connecting tube was immersed in water in the vacuum flask to provide a water trap for acid gases. The vacuum flask was connected through washing and drying tubes to a receiver flask immersed in Dry Ice. The washing tube was filled with A" Berl saddles and provided with a dropping funnelso that water could be trickled dropwise down through the saddles countercurrent'to incoming gases. The drying tube was packed with calcium chloride.

The preliminary heating section was heated to a temperature of 280 C., and the reactor was heated, the temperature being 515 C. and 494 C. at'two positions in the reactor. The dichlorofluoroethane was fed into the reactor at a constant rotameter reading. During the three-hour run, the preliminary heating temperature varied from 280 to 335 C., and the reactor temperatures from 494 to 520 C. The quantity of dichlorofluoroethane passed through was 1.865 moles (218 grams) for an average rate of 0.62 mole/hour. The pyrolysate collected in the receiver amounted to 153 grams. By titration, the water in the water trap was found to contain 1.6 gram equivalents of acid, and chloride analysis showed 1.49 gram equivalents of chloride ion.

The 153 grams of pyrolyzate was fractionated, using a low temperature still, and 97 grams of vinylidene chlorofluoride was distilled at 26.5 C. to -26 C., for a conversion of 64.5% of the material charged. After changing to a regular still with a low temperature head, the bulk of the remaining material distilled at 28 to 305 C. By refractive index it was determined that the higher boiling material contained 15.4 grams 1,1- dichloroethylene, i.e., vinylidene chloride, and 28.6 grams of the starting dichlorofluoroethane. The 97 grams of vinylidene chlorofluoride is a yield of 74% of theory,

based on unrecovered dichlorofluoroethane.

In the above run, the average rate of fiow would cause a unit volume of the dichlorofluoroethane or its conversion products to remain in the reactor tube for about 36 seconds.

The following table demonstrates the importance of reaction temperature and contact time in the production of vinylidene chlorofluoride by pyrolysis. Run 1 of the table is the run in Example 1 above, and the other runs were conducted in the same apparatus and with the same procedure.

3 T able.-Pyrlysis 0f 1,1-dichl0r0-I-flu0r0ethane Products Recovered, Per- CEO-F01, Average. Contact CHaGFClz cent Conversion Yield of R'un Feed; Reactor Time, Recovered, OH1=CFCL moles/hr. Temp, see: Bercent 5 Percent 0. .OH,=0FO1 CH1=CC1r 0.62 e00v as 12.9 64.5 8.6 74 1.85 500 12 44.8 39.5 7.6 71.5 e50 400 49 I our 12.4 7.7: 35.3 1.95 600 o 27.4 0 27.4

In. runl the conversion and yield were good. In run carbon. Moreover, the fluorination can be conducted 2, a shorter contact time not only lowered the conversion, under pressure in the absence of a catalyst, although this limit is notable that it did not improve the yield, and 15 procedure involves more costly apparatus and is more in fact resulted in a slightly lower yield. In run 3', a cumbersome to combine intoa continuous process with lower reaction temperature, eventhough coupled with a the pyrolysis reaction. longer contact time, resulted in poor conversion and a In the pyrolysis reaction the-vinylidene chlorofluoride poor yield. In run 4', a higher reaction temperature, product can be separated, and the remaining organic even with a short contact time, gave a poor conversion pyrolyzate (principally dichlorofluoroethane and 1,1-di-' and a poor yield. The absence of dichlorofluoroethane chloroethylene) can be recycled, alone, or mixed with and 1,1-di'ch1oroethylene from the pyrolysis product of additional dichlorofluoroethane, as will be understood by run 4' may have been caused by partial hydrolysis of: the those skilled in the art. The fact that the vinylidene reactor off gases. in the water trap. chlorofluoride boils about 50 to 55 C. lower than the I other pyrolyzate material makes recycling readily appli- 3600X273'XV bl t thi Contact ea c o sprocess.

22,400XNX T The pyrolysis reaction of the present invention is conwhich is the volume of the reactor inv milliliters, veniently conducted at or near atmospheric pressure,v but N is moles. per f d rate, T is the absolute it can also be conducted" at higher or lower pressures. temperamm The pyrolys1s reaction is particularly adapted to and use- EXAMPLE 2 ful for continuous flow systems.

' While it is ordinarily necessary to use the pyrolysis Methyl chloroform W charged y gfflvity'thfough temperature and reaction time conditions specified herein, rotameter into the reactor tube at a feed rate 0f it will'be recognized that these conditions'can be modified gram-equivalent per hour- At the S t anhydrous somewhat with varying pressures, heat transfer properhydrogen fluoride was charged at the rate of 2-18 g a ties of the reactor, or in the presence or absence of catafiqllival'ems P houf- The reactor tube Was filled With lysts. All of these modifications within the skill of the an aluminum fluoride catalyst packing. After four hours art are contemplated by the present invention; Among during which the reaction tube was maintained t the catalysts contemplated are cobalt, nickel, chromium, temperature around 100 C., the material Collected in 40 and other metals and any known dehydrohalbgenation the dry ice cooled receiver and the organic layer in catalysts, the water trap were fractionated by distillation. The A commercially feasible method of preparing vinyldistillation showed that 29.9% of the methyl chloroform idene chlorofluoride has been described. The method charged had been converted to l,l-dichloro-l-fluoroethane involves the fluorination of methyl chloroform to 1,1-di. of 96.5% purity, and that 62.8% of. the methyl chlorochloro-l-fluoroethane, and pyrolysis of the 1,1-dichloroform was recovered. Most of the impurity in the dil-fluoroethane to vinylidene chlorofluoride. cblorofluoroethane is 1,1-dichloroethylene which distills I claim: at about the same temperature, 29 to 31 C. The fact 1. The method of preparing vinylidene chlorofluoride thatthe amount of this impurity is small is particularly which comprises pyrolyzing 1,I-dichloro-l-fluoroethane at advantageous when it is desired to immediately pyrolyzc a temperature of 465 to 535 C. to convert a substantial the dichlorofluoroethylene without further purification. portion of said 1,1-dichloro-l-fluoroethane to vinylidcne As the methyl chloroformboils at 74.1 C., the dichlorochlorofluoride. fluoromethane can be readily separated therefrom by dis- 2. The method of preparing vinylidene chlorofluoride tillation, and subjected to the pyrolysis reaction, while which comprises pyrolyzing 1,1-dichloro-1-fluoroethane the methyl chloroform is recycled throught the fluorinator. at a temperature of 465 to 535 C. for 25 to 45 seconds. This combination. of fluorination and pyrolysisreactions 3. The method of preparing'vinylidene chlorofluoride is particularly useful as a continuous flow process- The which comprises pyrolyzing material consisting of. 1,1- aluminum fluoride catalyzed fluorination not only gives dichloro-l-fluoroethane at a temperature of about 500 a dichlorofluoroethane product of good purity, but'it re- C. for about 36 seconds in a nickel tube packed with sults' in a yield of 80.4% of theory, based on unrecovered nickel particles. methyl chloroform, 7

While vapor phase fluorination over aluminum fluoride, Rfiemces Cited in file of this P AIF is preferred, particularly. at temperatures of 90 to .UNITED STATES PATENTS 125 C. for 5 to 20 seconds, the fluorination canalso. be conductedover stannic fluoride on activated carbon. 2 3i; 2 These two catalyst systems are ordinarily used at tem- 2628989 ey e peratures of 60 to 125 C. for contact times of 5 to 2673139 I 1"; f 1953, 60 seconds. It will be recognized that the optimum con- 2,709,688 9 1954 tact times will usually vary inversely with the reaction an May 1955 temperatures; Effective fluorination conditions arev fur- V FOREIGN PATENTS ther' described in my aforementioned cop'ending application, Serial No. 565,777, filed February 16, 1956. 67030 a 1939 Other. and less desirable catalysts which can be used REFERENCES for the" fluorination reaction are antimony pentafluoride Torkington et al.: .Trans'. Faraday. Soc, vol. '41 on activated carbon and antimony trifluon'de on activated (1945), page 237; V 

1. THE METHOD OF PREPARING VINYLIDENE CHLOROFLUORIDE WHICH COMPRISES PYROLYZING 1,1-DICHLORO-1-FLUOROETHANE AT A TEMPERATURE OF 465 TO 535*C. TO CONVERT A SUBSTANTIAL PORTION OF SAID 1,1-DICHLORO-1-FLUOROETHANE TO VINYLIDENE CHLOROFLUORIDE. 